Metal recovery



March 14, 1939. G|LBERT 2,150,437

METAL RECOVERY Original Filed Feb. 2, 1933 INVENTOR. HARVEY ".CflLBERT MZAM ATTORNEY Patented Menu, 1939 mire-o sTATss PATENT caries METAL RECOVERY Harvey N. Gilbert, Niagara Falls, N. 'Y.,

assignor to E. I. du Pont de Nemcurs & Company, Incorporated, Wilmington, Deb, a corporation of Delaware Original application February 2, 1933, Serial No.

654,844, now Patent No. Divided any 4, 1936.

2,029,998, dated Feband this application 111 August 15, 1935, Serial No. 36,360

a claims. lei. 210-57 lithium, etc., the alkaline earth metals, 1. e. calcium, barium, strontium, and magnesium and beryllium. In the production of light metals by electrolysis of fused metal'salts, the crude metal as obtainedfrom the electrolytic cell usually contains a.- number of solid impurities, consisting mainly of metal salts and oxides. The crude metal is usually purified by mechanical separa-, tion of solid impurities, for instance by filtration of the molten metal. The residue obtained from such separation consists of a mixture of the separated solids suspendedyin or emulsified with more .or less liquid metal.

peering in the residue may vary, depending upon the nature of the metal and the method of purification used, and in some cases may be as much as 90% by weight. The separation of any significant' amount of metal from such residues heretofore has been exceedingly difiicult; and a complete separation of metal from the non-metallic substances presenthas been heretofore impossible.

If a partial separation be efiected', for example by pressing, the final residue still contains consider.- able-amounts of metal and if the metal is of the more reactive type, for instance sodium, the residue is hazardous to handle and dispose of because of the danger of fire if it should come in contact with water or atmospheric moisture. Such residues can be disposed of only by destroying the metal, by burning in a furnace or by other chemical means. When this is done, the

" resulting mixture of salts and oxides has no comamounts of calcium.

mercial value and must be wasted.

In some cases where a foreign salt is used to lower the melting point of the electrolyte in the production of a light metal by fused salt electrolysis, more or less of the-corresponding foreign metal also appears in the crude metal-removed from the cell. For example, in the production of,

sodium by electrolysis of fused sodium chloride, calcium chloride is added, to the electrolyte with the result that the crude sodium contains small In cases where the foreign metal is of limited solubility in the metal being completely recover metal values from the aforethat object is The amount of metal ap-.

produced, it may be removed from the liquid mixture along-with thenon-metallic impurities by mechanical separation at a temperature below the freezing point of the foreign metal. In such cases, the residue obtained consists of considerable amounts of this foreignmetal, mixed with the other salts and metals and oxides of one or both of the metals. I

' An object of this invention is to substantially said residues obtained in the separation of solid impurities from electrolytic light metals. Aimto effect such recovery in such manner that non-metallic by-products of commeroial value will be obtained. A still further object is to provide an improved means for reacting a light metal mixture or alloy with a salt or .salt'mixture to produce a different metal or alloy.

Other objects will be hereinafter apparent.

I have discovered that essentially complete separation of metal from mixtures of the nature of the aforesaid residues may be accomplished by introducing the residues into a separating bath at f a temperature at which the metal to be recovered is liquid. The separating bath of my invention is a body of molten salt having a specific gravity materially higher than that of the metal. When such residues are added to the separating bath, the salts and oxides of the residues dissolve or settle out in the molten salt'while the metal or metals rise to the surface thereof, and may be drawn ofi in the liquid state or othe as removed, thus eiiecting a substantially complete separation of the metal from the non-metallic substances present. If it is desired merely to 55 effect a mechanical separation of light metal from non-metals without changing the amount or nature of the metal or alloy originally present, the separating bath is made up of salts with which the metal residues will not react. On the other 4 hand, the composition of the fused salt separating v bath may be so selected that one or more metals present in the residue will react with one or more constituents of the fused salt separating bath to produce another metal or alloy, this reaction being effected simultaneously with the separation of the non-metallic constituents.

One modification of my invention comprises contacting a residue containing more than one metal with a fusedsalt or salt mixture which re acts with all but one of the metals, so that the metal or alloy finally removed from the system is substantially free from the undesired metalor metals or contains a smaller proportion of them than was present in the original mixture. 55

'a certain angular 'tact with molten salt, which For example, a residue containing two metals may be reacted with a salt of one of them. The metal whose salt is not originally present in the molten salt bath will react by double decomposition with the salt to release the metal of the salt in its stead, and the metal rising towards the surface of the salt bath will be substantially pure or will contain less of the metal which reacts with the salt of the separating bath than was originally present, depending upon circumstances more fully described below.

The appended drawing illustrates diagrammatically two forms of apparatus which may be utilized to carry out myinvention.

Fig. 1 shows in cross section a covered vessel I filled with a molten separating salt bath and heated by means not shown. Arranged within vessel I in such manner that it lies below the surface of the fused salt is a cylindrical, inverted bell 2. An inlet tube 3 passes through the cover of the vessel I and thence through the top of the bell 2 to a point near but above theopen end of the bell. An outlet tube 4 leads from the top of the bell to the exterior of vvessel I.

The apparatus illustrated by Fig. 2 is identical with that illustrated by Fig. 1 as respects the vessel I, the bell 2, the inlettube 3 and the outlet tube 4, but has in addition a settling trap 5 connected to the outlet 4. Settling trap 5 is elongated in shape and has a downwardly extending member or sump 1 at the end opposite the connection to outlet 4. Scraping tool 6, which is inserted through the wall of trap 5 in such manner that it is capable of reciprocal motion and displacement, is adapted to scrape solid'material from the bottom of trap 5 into sump I. An opening, closed by cover 9, is situated in trap 5 directly above the sump 1. Outlet, pipe 8 serves to carry liquid metal from trap 5.

One method of carrying out my invention may be described by reference to Fig. 1. A residue consisting of a sludge-like mixture of molten light metal or metals and insoluble non-metallic substances, e. g. salts and oxides, is introduced into the apparatus continuously through inlet 3. At the bottomof inlet 3, the residue comes into condissolves certain of the non-metallic impurities; other impurities settle out, while metal substantially free from non-metallic substances collects in the upper portion of'bell 2. Due to the diflerence between the specific gravities of the salt and the metal, the metal is forced upwards through outlet 4, where it maybe collected in suitable containers, molds or the like. Preferably, the portion of the salt bath below bell 2 is lightly agitated, e. g. by a current of gas inert to the metal being recovered, so as to prevent large amounts of the insoluble solid material from settling out in the bottom of vessel I; otherwise, there is a tendency for settled solids, which are heat insulators, to cause overheating of the bottom of the vessel. At intervals, accumulated solids may be allowed to settle out and then removed. The temperature of the molten bath, of course, must be above the melting desired to obtain 'At the start of the operation,

'flowing sodium. Trap 5 outlet tube be correspondingly shortened.

In some cases, as mentioned above, the residues entering the process will contain more than one free light metal. The method of handling such residues according to my invention where it is only one of the metals present, is illustrated by the following example:

Ezra mple The process is carried out in the apparatus diagrammatically illustrated by Fig. 2 of thedrawing. Vessel I is a covered steel cylindrical pot, for example, 10 feet deep by 4 feet in diameter. The bell 2 is 24 inches in diameter by 4 feet 6 inches; long,the top of the bell being situated about 17 inches below the cover of vessel I. Inlet 3 is a 4-inch iron pipe 6 feet 6 inches in length, extending to within 18 inches of the bottom of the bell 2. Settling trap 5 is a cylindrical vessel 16 inches in diameter by 7 feet 3 inches in length, the downwardly extending member I being 16 inches in diameter by about 12 inches in length.

Vessel l is mounted in a furnace heated by a gas flame and is filled to a point above the top of hell 2 with a fused, anhydrous mixture of calcium chloride and sodium chloride, containing between 60 and 75% by weight of sodium chloride. A filter residue, containing about 70% of metallic sodium, about 20% of metallic calcium, and about 10% of salts and oxides of these metals, is contends to settle in the lower portion of the bath;

the calcium reacts with the salt bath 'as follows:

Ca+2NaCl- 2Na+CaCla I the temperature of the bath in vessel I is maintained at between 700 and 800 C.; later, as the sodium chloride content of the bath decreases, due to the reaction between calcium and sodium chloride, the melting point of the salt mixture is correspondingly lowered and the temperature may be reduced to around 600 the molten bath are removed from vessel I from time to time and analyzed to determine the sodium chloride and calcium oxide contents. The sodium chloride content of the. bath is maintained at not less than 30% by weight by withdrawing portions of the' bath and replacing themby sodium chloride as necessary. When the calcium oxide content reaches 10-20% 4 rises above the salt bath level must C. During the process, samples of by weight, 'agitation is interrupted and when the oxide has settled metal leaves bell 2, substantially all of any unreacted calcium present is dissolved in the outis air-cooled, preferably by blowing a blast of air against the exterior surface, to cool the metal therein to a temperature of to 175 C. Preferably, the temperature in trap 5 is maintained so that the temperature of the sodium leaving at exit pipe 8 is between and C. At these temperatures, the calcium precipitates and settles out in the bottom of the trap- At regular intervals of time, for instance every fifteen minutes, the calcium settling out in the bottom of the trap is scraped into the sump 1 by means of the scraper 6. From time to time, the precipitated calcium is removed from sump I by a bailing device inserted into the apparatus by way of the opening closed by cover 19: The material thus removed consists of a mix- The sodium issuing ture' of sodium and calcium, containing a small amount of oxide, nd may be recycled through the process by'introducing it by way of inlet 3. from the apparatus by way of outlet 8 is substantially free from oxide and] or Y salt and may be substantially free from calcium or may contain up on how emciently out. Samples of to 1% of calcium, depending the process has been carried from the above residue had-the following comsalt bath employed, the composition of the metal issuing from the process may be correspondingly varied. For example, by varying the calcium chloride content of the salt bath described in the above example, sodium-calcium alloys of various compositions may be produced. If it is desired to produce an alloy chloride content of the bath is maintained at a high value, e. g. more than 70% by weight,

whereupon the following reaction will occur:

The process advantageously can be used to recover a substantially pure light metal from a mixture, not only by completing the separation in a settling trap or other'mechanical means as illustrated by the above example, but by eflfecting a complete separation by means of reaction with the molten salt separating bath, utilizing a series of runsif necessary. ture of sodium and. calcium, either pure or comtaminated with non-metallic substances, may be points.

The temperature at which the process is carried out depends upon the respective melting points of the salts and metals and also to some extent upon the relative viscosity of the molten salts and metals at various temperatures above their melting point. That is, the metals and salts present must be sufliciently fluid at the operating temperature to permit.

eflective gravity separation of the bath components.

sodium obtained by this process preparation rich in calcium, the calcium For example, a mixinvolved in the process,

- Preferably the fused salt bath is maintained substantially free from watenesp'ecially if highly reactive metals such as sodium are present. However, small amounts of water, maybe present, provided the resulting hydrogen evolution is not excessive. I

My process, is useful and advantageous in many respects. It permits efllcient, economical, and effective separation of light metals from each other or from non-metallic impurities, and efiects such separations more efficiently and eco nomically than has heretofore been possible. The process also is useful and eificient for the preparation of various alloys f the light metals from-various light metal mixtures. 4- An advantage of the process, as applied to the electrolytic of light metals, is that it converts impurities in the crude product into a salt mix ture suitable for partial replenishing of the V electrolytic cell bath.

Iclaim:

'1. An apparatus comprising a yertical cylindrical covered tank filled 'th a molten salt mix ture, an inverted, ll-shaped' separator open at the lower end submerged beneath the'surface of said molten salt mixtureinthe upper portion of said tank, the volume capacityoff said separator being approximately one-tenth of the volume capacity of said tank, inlet means-for introduc-' ing a mixture of light metals extending into said separator to a point near the lower end thereof and outlet means connected to the top of said separator and leading tank. p

2. An apparatus for separating sodium from a mixture of sodium, calciumand oxide comprising a vessel containing a molten salt mixture comprising a sodium salt, an inverted bell submerged beneath the a' settling chamber located above the surface of said salt mixture and connected by a conduit with the upper portion of said bell, means for cooling said settling chamber, an outlet pipe connected to the upper portion of said settling chamber at a point remote through the cover of said surface of said salt mixture in the upper portion oi said chamber, an inlet tube opening into the lower portion of said bell,

from said conduit and means for removing solid material from the 1 bottom of said settling chamber.

3. An apparatus for separating a light metal from a pasty mixture of molten light metals and non-metallic impurities comprising a vessel containing a molten salt of at least one of said light metals, an inverted bell located beneath the surface of said molten said vessel, an inlet means adapted to lead said pasty mixture of light metals into thelower portion ofsaid bell, a conduit for, leading molten metal alloy from the upper portion of said bell to a point above the surfaceof said molten salt,.

a settling chamber connected to saidconduit,

means for cooling said settling chamber and an outlet adapted to lead molten metal from the upper portion of said settling chamber at a point remote from said conduit- HARVEY N. GILBERT.

salt in the upper portion of I 

